U.S. patent number 5,120,783 [Application Number 07/613,989] was granted by the patent office on 1992-06-09 for stabilized halogen-containing resin compositions.
This patent grant is currently assigned to Kyowa Chemical Industry Co., Ltd.. Invention is credited to Shigeo Miyata, Tsutomu Nosu.
United States Patent |
5,120,783 |
Nosu , et al. |
June 9, 1992 |
Stabilized halogen-containing resin compositions
Abstract
A stabilized halogen-containing resin composition wherein (a)
0.01 to 10 weight parts of da hydrotalcite, (b) 0.01 to 5 weight
parts of a zinc compound, (c) 0.01 to 5 weight parts of magnesium
hydroxide, and (d) 0.01 to 5 weight parts of a .beta.-diketone
compound and/or a phosphite compound are compound into a
halogen-containing resin per 100 weight parts thereof and a molding
article therefrom.
Inventors: |
Nosu; Tsutomu (Takamatsu,
JP), Miyata; Shigeo (Takamatsu, JP) |
Assignee: |
Kyowa Chemical Industry Co.,
Ltd. (Kagawa, JP)
|
Family
ID: |
17829478 |
Appl.
No.: |
07/613,989 |
Filed: |
November 15, 1990 |
Foreign Application Priority Data
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Nov 16, 1989 [JP] |
|
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1-296126 |
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Current U.S.
Class: |
524/357; 524/147;
524/151; 524/351; 524/424; 524/432; 524/434; 524/436 |
Current CPC
Class: |
C08K
3/22 (20130101); C08K 3/26 (20130101); C08K
5/07 (20130101); C08K 5/098 (20130101); C08K
5/524 (20130101); C08K 3/22 (20130101); C08L
57/08 (20130101); C08K 3/26 (20130101); C08L
57/08 (20130101); C08K 5/07 (20130101); C08L
57/08 (20130101); C08K 5/098 (20130101); C08L
57/08 (20130101); C08K 5/524 (20130101); C08L
57/08 (20130101) |
Current International
Class: |
C08K
3/00 (20060101); C08K 3/22 (20060101); C08K
5/00 (20060101); C08K 3/26 (20060101); C08K
5/098 (20060101); C08K 5/524 (20060101); C08K
5/07 (20060101); C08K 005/526 (); C08K
005/07 () |
Field of
Search: |
;524/424,432,434,351,436,357,437,147,151 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0256872 |
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Feb 1988 |
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EP |
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0362012 |
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Apr 1990 |
|
EP |
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Primary Examiner: Hoke; Veronica P.
Attorney, Agent or Firm: Wenderoth, Lind & Ponack
Claims
We claim:
1. A stabilized halogen-containing resin composition wherein
(a) 0.01 to 10 weight parts of a hydrotalcite,
(b) 0.01 to 5 weight parts of at least one zinc compound selected
from the group consisting of an organic carboxylic acid zinc salt,
zinc oxide, a basic carbonate salt and zinc carbonate,
(c) 0.01 to 5 weight parts of magnesium hydroxide having an average
secondary grain size of 2 .mu.m or less and a specific surface area
of 15 m.sup.2 /g or more, and
(d) 0.01 to 5 weight parts of a .beta.-diketone compound and/or a
phosphite compound selected from the group consisting of a
bisphenol A tetra C.sub.12-15 alkyl diphosphite, triisodecyl
phosphite or phenyl diisodecyl phosphite are compounded into a
halogen-containing resin per 100 weight parts thereof.
2. The resin composition of claim 1 wherein
(a) 0.1 to 10 weight parts of a hydrotalcite,
(b) 0.05 to 1 weight parts of said zinc compound,
(c) 0.05 to 1 weight parts of said magnesium hydroxide, and
(d) 0.05 to 1 weight parts of a .beta.-diketone compound and/or
said phosphite compound are compounded into a halogen-containing
resin per 100 weight parts thereof.
3. The resin composition of claim 1 or 2 wherein the
halogen-containing resin is at least one polymer selected from the
group consisiting of a vinyl chloride polymer, a vinyl
chloride/vinyl acetate copolymer, a vinylidene chloride copolymer,
a post-chlorinated vinyl chloride polymer, chlorinated polyethylene
and chlorinated polypropylene.
4. The resin composition of claim 1 or 2 wherein the hydrotalcite
is represented by the following general formula (1)
wherein M.sup.+2 is Mg or a mixture of Mg and Zn, A.sup.n-
represents one or more of n valent anions, x is a positive number
satisfying 0.2.ltoreq.x<0.5, and m is a positive number
satisfying 0<m<1.
5. The resin composition of claim 4 wherein the hydrotalcite is one
obtained by substantially removing the crystallition water by
heating a hydrotalcite represented by the above general formula (1)
at a temperature of 200.degree. to 300.degree. C.
6. The resin composition of claim 1 or 2 wherein the
.beta.-diketone compound is stearoylbenzoylmethane.
7. A molding article from the resin composition of claim 1 or 2.
Description
DETAILED DESCRIPTION OF THE INVENTION
1. Industrially Applicable Field
This invention relates to a stabilized halogen-containing resin
composition. More detailedly, this invention relates to a
halogen-containing resin composition having restrained initial
coloring, high transparency and excellent heat stability, wherein
(a) a hydrotalcite, (b) a zinc compound, (c) magnesium hydroxide,
and (d) a .beta.-diketone compound and/or a phosphite compound are
compounded into a halogen-containing resin.
2. Prior Art
Halogen-containing resins are unstable against light, and
especially when heat melt molding is carried out, decomposition
takes place accompanied by generation of hydrogen halide. As a
result, the arise disadvantages, for example, that the resin is
colored or its mechanical strength lowers. For solution of such
disadvantages, a compound of a metal such as Cd, Sn, Pb, Ca, Ba or
Zn has necessarily been added as a stabilizer to the
halogen-containing resin before the thermal molding and processing,
and thus the purpose has been attained.
However, recently, the toxicity of compounds of Cd, Pb and Ba has
come to become a social problem, and particularly, use of compounds
of Cd and Pb either has almost been prohibited, or is only
permitted in extremely limited fields. Further, also as for
compounds of Sn, their addition quantities are restricted in view
of toxicity, and further they have a drawback of being
expensive.
Compounds of Ca and Zn have advantages of extremely low toxicity
and cheapness, but have, when compounded into a halogen-containing
resin, disadvantage that only a small extent of improvement effects
of transparency and heat stability are obtained.
On the other hand, when, as proposed by one of the present
inventors, a stabilizer containing as a main component a
hydrotalcite is added to the resin (refer to U.S. Pat. No.
4,085,088), the resulting resin composition has only very small
toxicity, and further are excellent in transparency and heat
stability. Therefore, the technique has drawn attention in many use
fields, and their use has enlarged.
However, hydrotalcites have a drawback that, when added to
halogen-containing resins, they color the resins to red group
color. It was proposed as an improvement method of this coloring to
compound into a hydrotalcite a combination of zinc and a
.beta.-diketone compound (refer to U.S. Pat. No. 4,427,816).
According to this proposal, the initial coloring of the
halogen-containing resin was improved. In this proposal, when a
hydrotalcite is used after being heated to about 200.degree. to
300.degree. C. to remove crystallization water, there arises
effects that the initial coloring is reduced, and moreover, when
the resin composition is molded and processed at a temperature of
200.degree. C. or more, the trouble of foaming is reduced or
obviated.
3. Problems to be solved by the Invention
However, the improvement in the above U.S. Patent caused another
problem that the excellent heat stability is somewhat reduced which
the resin composition inherently possessed when a hydrotalcite was
compounded therein. This reduce in heat stability tends to occur
particularly strikingly when the above hydrotalcite after the
crystallization water removal treatment is used. This tendency
becomes greater in proportion as the addition amount of the zinc
compound effective to reduce the initial coloring increases. On the
other hand, the .beta.-diketone compound used together with zinc
compound is expensive. Thus, it is desirable to increase the
addition amount of the cheap zinc compound and use the expensive
.beta.-diketone compound at an as small amount as possible.
Means for Solving the Problems
The present inventors studied for the purpose of improving the
lowering of heat stability inherently possessed by a hydrotalcite
which lowering occurs when a zinc compound and a .beta.-diketone
compound are used together in order to solve the drawback of the
initial coloring when the hydrotalcite, particularly the
hydrotalcite after being subjected to the treatment of removal of
crystallization water with heating is incorporated as a stabilizer
in a halogen-containing resin. As a result, they found that the
above purpose can be attained by further compounding
microcrystalline and highly dispersible magnesium hydroxide. It was
found that, by compounding of such magnesium hydroxide, the
lowering of heat stability as the problem can remarkably be
improved with hardly impairing the advantage of non-toxicity and
transparency inherently possessed by the hydrotalcite and with
hardly having a bad influence on the prevention of initial coloring
by the zinc compound and the .beta.-diketone compound.
In addition, it was found the phosphite compounds have the same
action with .beta.-diketone compounds.
Thus, according to this invention, a stabilized halogen-containing
resin composition is provided wherein
(a) 0.01 to 10 weight parts of a hydrotalcite,
(b) 0.01 to 5 weight parts of zinc compound,
(c) 0.01 to 5 weight parts of magnesium hydroxide, and
(d) 0.01 to 5 weight parts of a .beta.-diketone compound and/or a
phophite compound
are compounded into a halogen-containing resin per 100 weight parts
thereof.
Such halogen-containing resin compositions of the invention have
the characteristic and advantage that they can be utilized over
extremely wide fields from fields of medical applicances, food
packing, food vessels, etc. where stability of an extremely high
level is required to fields of automobile parts, miscellaneous
goods, etc. where non-toxicity is not so required.
Furthermore, halogen-containing resin compositions of the invention
exhibit only a low extent of initial coloring and are excellent in
transparency and heat stability. Therfore, halogen-containing resin
compositions of the invention are particularly excellent as
materials of medical appliances, food vessels, food packing, film,
cosmetic vessels, etc.
The halogen-containing resins in resin compositions of the
invention include homopolymers on copolymers of a
halogen-containing monomer, halides of a polymer, etc. Examples of
such halogen-containing resins include vinyl chloride polymers,
vinyl chloride/vinyl acetate copolymers, vinylidene chloride
polymers or copolymers, post-chlorinated vinyl chloride polymers,
chlorinate olefin polymers such as chlorinated polyethylene and
chlorinated polypropylene, and the like.
The hydrotalcite (a) compounded in the above halogen-containing
resin composition in the invention is a hydrotalcite represented by
the following formula (1)
(wherein M.sup.+2 is Mg or a mixture of Mg and Zn, A.sup.n-
represents one or more of n valent anions, x is a positive number
satisfying 0<X<0.5, and m is a positive number satisfying
0.ltoreq.m.ltoreq.1) or a compound having an analogous crystal
structure thereto.
In the hydrotalcite of the above general formula, ClO.sub.4.sup.-,
CH.sub.3 COO.sup.-, CO.sub.3.sup.2- or the like is mentioned as the
n valent anion of A.sup.n-. Further, it is preferred that x is a
positive number satisfying 0.2.ltoreq.x.ltoreq.0.5, particularly
0.3.ltoreq.x.ltoreq.0.4.
It is preferred that the hydrotalcite of the above formula to be
used is one whose crystallization water was almost removed by
heating at a temperature of about 200.degree. to 300.degree. C. for
about several hours to ten and several hours for the purpose of the
desired further reduction of the initial coloring and realization
of transparency as well as for the purpose of preventing foaming at
the time of processing and molding at about 200.degree. C. or more.
That is, the hydrotalcite whose crystalization water was removed
corresponds to the hydrotalcite of the above formula wherein m is
0.
It is preferred that a hydrotalcite to be used in the invention is
one wherein crystals are developed relatively well and which
exhibits only a low extent of aggregation. The BET specific surface
area as a representative indicating the size of crystals is
preferably in the range of about 10 to 30 m.sup.2 /g, and the
secondary grain size is suitably about 2 .mu.m or less, preferably
1 .mu.m or less.
Suitable hydrotalcites used in the invention are, for example,
hydrotalcites disclosed in the specifications of U.S. Pat. Nos.
3,539,306, 3,650,704, 3,796,792, 3,875,525, 3,879,523 and 4,085,088
and those obtained according to the preparation processes
therein.
On the other hand, in order to improve the dispersibility of the
hydrotalcite in the resin, it is preferred to previously cover its
crystal surface with an anion surfactant, a silane coupling agent,
a titanate coupling agent, an aluminum coupling agent, an acid
phosphite or the like. The compounding amount of the above
hydrotalcite is 0.01 to 10 weight parts, preferably 0.1 to 5 weight
parts, particularly preferably 0.2 to 2 weight parts per 100 weight
parts of the halogen-containing resin.
Zinc salts of the following organic acids are preferably used as
the zinc compounds (b) in the invention. Specific examples of
organic acids forming zinc salts include monovalent carboxylic
acids having 2 to 40 carbon atoms such as acetic acid, propionic
acid, butyric acid, valeric acid, caproic acid, enanthic acid,
caprylic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic
acid, carpryl acid, undecanoic acid, lauric acid, tridecanoic acid,
lauric acid, tridecanoic acid, myristic acid, palmitic acid,
isostearic acid, stearic acid, 1,2-hydroxystearic acid, behenic
acid, montanic acid, benzoic acid, monochlorobenzoic acid,
p-tert-butylbenozic acid, dimethylhydroxybenzoic acid,
3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid,
dimethylbenzoic acid, ethylbenzoic acid, cuminic acid,
n-propylenzoic acid, aminobenzoic acid, N,N-dimethylbenzoic acid,
acetoxybenozic acid, salicylbenzoic acid, p-tert-octylsalicylic
acid, oleic acid, elaidic acid, linoleic acid, linolenic acid,
thioglycolic acid, mercaptopropionic acid and
octylmercaptopropionic acid; monoester or monoamide compounds of
divalent carboxylic acids having 2 to 40 carbon atoms such as
oxalic acid, malonic acid, succinic acid, glutaric acid, adipic
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
phthalic acid, isophthalic acid, tetraphthalic acid, oxyphthalic
acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric
acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid
and thiodipropionic acid; di- or triester compounds of trivalent or
tetravelent carboxylic acids having 5 to 40 carbon atoms such as
hemimellitic acid, trimellitic acid, mellophanic acid, pyromellitic
acid and mellitic acid; etc. Besides the above organic acid salts
of zinc, inorganic zinc compounds such as zinc oxide, basic zinc
carbonate and zinc carbonate can also be used.
The use amount of such a zinc compound (b) is 0.01 to 5 weight
parts, preferably 0.05 to 1 weight parts, particularly preferably
0. to 0.5 weight part per 100 weight parts of the halogen
containing resin.
It is desired for improvement of heat stability and transparency
that magnesium hydroxide (c) used in the invention is a composed of
small crystals and their secondary grains are small. Crystal size
represented in terms of BET specific surface area is 15 m.sup.2 /g
or more, particularly preferably 2 m.sup.2 /g or more. The average
secondary grain size is 2 .mu.m or less, preferably 1 .mu.m or less
and particularly preferably 0.5 .mu.m or less. It is preferred, in
order to improve the dispersibility of magnesium hydroxide in the
resin, to use a surface treating agent of the hydrotalcite
similarly.
Compounding amount of the above magnesium hdyroxide (c) is 0.01 to
5 weight parts, prefeably 0.05 to 1 weight part and particularly
preferably 0.1 to 0.5 weight part per 100 weight parts of the
halogen-containing resin.
.beta.-Diketone compounds (d) used in the invention are compound
represented by the following formula (2)
wherein R.sub.1 and R.sub.3 may be the same or different and each
represent a straight-chain or branched alkyl or alkenyl group
having up to 30 carbon atoms, an alkyl group having 7 to 36 carbon
atoms, or an aryl or alicyclic group having less than 14 carbon
atoms (the alicyclic group can optionally contain carbon-carbon
double bond(s), and one of the two may be a hydrogen atom), and
R.sub.2 represents a hydrogen atom, or an alkyl or alkenyl having
up to 30 carbon atoms.
Specific examples of such .beta.-diektone compounds (d) include,
for example, dehydroacetic acid, dehydropropionylacetic acid,
dehydrobenzoylacetic acid, cyclohexane-1,3-dione, dimedone,
2,2'-methylenebiscyclohexane-1,3-dione,
2-benzylcyclohexane-1,3-dione, acetyltetralone, palmitoyltetralone,
stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone,
2-benzoylcyclohexanone,
2-acetyl-cyclohexanone- 1,3-dione, benzoyl-p-chlorobenzolymethane,
bis(4-methylbenzoyl)methane, bis(2-hydroxybenzoyl)methane,
benzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane,
stearoyl-benzoylmethane, palmitoyl-benzoylmethane,
dibenzoylmethane, 4-methoxybenzoly-benzoylmethane,
bis(4-chlorobenzoyl)methane, bis(3,4-methylenedioxybenzol)methane,
benzoyl-acetyl-octylmethane, benzoyl-acetyl-phenylmethane,
stearoyl-4-methoxybenzoylmethane, bis(4-t-butylbenzoyl)methane,
benzoylacetyl-ethymethane, benzoyl-trifluoro-acetylmethane,
diacetylmethane, butanoyl-acetylmethane, heptanoyl-acetylmethane,
triacetylmethane, distearoylmethane, stearoyl- acetylmethane,
palmitoyl-acetylmethane, lauroyl-acetylmethane,
benzoyl-formylmethane, acetylformyl-methylmethane,
benzoyl-phenylacetylmethane, bis(cyclohexanoyl)methane, etc.
Further, metal salts of these .beta.-diketone compounds, for
example, salts thereof with metals such as lithium, sodium,
potassim, magnesium, calcium, barium, zinc, zirconium, tin and
aliuminum can similarly be used.
Particulrly preferred among the aobve .beta.-diketone compounds (d)
are stearoyl-benzolymethane and dibenzoylmethane.
The phosphite compounds (d) used in the invention is a compound
(monophosphite) represented by the following formula (3) ##STR1##
(wherein R.sub.4, R.sub.5 and R.sub.6 are the same or different
with one another and each represent an alkyl group having 1 to 20
carbon atoms or an aryl group having 6 to 14 carbonatoms), a
compound of the formula (3) wherein two of the substituents form a
ring, or a compound of an oligomer structure (oligophosphite)
wherein substituents of plural molecules of the formula (3) are
mutually intermolecularly linked.
Specific examples of phosphite compounds (d) include, for example,
triarylphosphites such as triphenyl phosphite, tris(nonylphenyl)
phosphite, tris(o-cyclohexylphenyl) phosphite, tris(p-nonylphenyl)
phosphite, monononylphenyl dinonylphenyl phosphite, phenyl
p-nonylphenyl phosphite and tris(2,4-di-t-butylphenyl) phosphite;
alkyl aryl phosphites such as isooctyl diphenyl phospite isodecyl
diphenyl phosphite lauryl diphenyl phosphite, phenyl diisodecyl
phosphite and phenyl dilauryl phosphite; trialkyl phosphites such
as triisooctyl phosphite, triisodecyl phosphite, trilauryl
phosphite and trioleyl phosphite; oligophosphites such as bisphenol
A tetra C.sub.12-15 alkyl diphosphite (trade name: "MARK 1500"),
distearyl pentaerythritol diphosphite,
2-t-butyl-2-(3-t-butyl-4-hydroxyphenyl) p-cumenylbis(p-nonylphenyl)
phosphite, diisodecyl pentaerithritol diphosphite and dinonyl
phenyl pentaerythritol diphosphite; etc.
Preferred among the above phosphite compounds (d) are bisphenol A
tetra C.sub.12-15 alkyl diphosphite, triisodecyl phosphite and
phenyl diisodecyl phosphite, and particularly preferred is
bisphenol A tetra C.sub.12-15 alkyl diphosphite.
The above .beta.-diketone compound and/or phosphite compound are/is
compounded in the rate of 0.01 to 5 weight parts, preferably 0.05
to 1 weight part per 100 weight parts of the halogen-containing
resin.
The halogen-containing resin composition of the invention may
further contain, besides the aforementioned components (a) to (d),
other components usually used as additives for resins, particularly
halogen-containing resins. These other additives include, for
example, a heat stabilizer, a plasticizer, an antioxidant, an
ultraviolet absorber, an antistatic agent, a lubricant, a coloring
agent, an impact improver, etc. Specific example of these additives
are described below.
(1) Heat stabilizers
There can, for example, be mentioned metallic soap heat stabilizers
such as metallic soaps of Ca, Mg or Ba with an aliphatic acid such
as 2-ethylhexoinic acid, lauric acid, myristic acid, palmitic acid,
stearic acid, hydroxystearic acid, linolic acid, behenic acid,
isostearic acid, oleic acid or ricinoleic acid; composite metallic
soap heat stabilziers such as composite metallic soaps of Ca/Zn or
Ba/Zn with one of the above alipahtic acids; epoxy compound heat
stabilziers such as epoxidized soybean oil, epoxidized linseed oil
aliphatic acid butyl, epoxidized linseed oil, epoxidized
1,2-polybutadiene, bisphenol 4-diglycidyl ether,
3,4-epoxycyclhexylmethyl and 3,4-epoxycyclohexanecarboxylate;
polyol heat stabilziers such as pentaerythritol, mannitol, xylitol,
sorbitol, glycerol, trimethylolpropane, polyethylane glycol,
polyvinyl alcohol and sorbitan monolaurate; aminocarboxylic acid
heat stabilizers such as butanediol .beta.-aminocrotonic acid
ester, N-acetylglutamine acid and N-acetylmethionine; sulfur
compound-containing heat stabilizers such as
dilauryl-thiodipropionate and 6-anilino-1,3,5-triazine-2,4-dithiol;
organic antimony heat stabilizers such as dibutylantimonymercapto
type, dibutylantimony laurate type, dibutylantimony maleate type,
di-n-octyl-antimonymercapto type, di-n-octylantimony maleate type
and di-n-octylantimony laurate type oraganic antimonies;
nitrogen-containig heat stabilizers such as urea, melamine,
.alpha.-phenylindole, diphenylthoiurea and tris(2-p-hydroxyethyl)
isocyanurate; etc.
(2) Plasticizers
There can, for example, be mentioned phosphoricacid ester
plasticizers such as tributyl phosphate, triphenyl phosphate and
tris(2-ethylphexyl) phosphate; phthalic acid ester plasticizers
such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate
and diisodecyl phthalate; aliphatic monobasic acid ester
plasticizers such butyl oleate, glycerol monooleic acid ester,
butyl stearate and butyl epoxystearate; aliphatic dibasic acid
ester plasticizers such as diisodecyl adipate, dibutyl adipate and
di-2-ethylphexyl adipate; dihydric alcohol ester plasticizers such
as diethylene glycol benzoate; oxyacid ester plasticizers such as
methyl acetyl ricinoleate; chlorinated paraffin plasticizers; wax
plasticizers such as waxes, low molecular weight polystyrenes and
liquid paraffin; etc.
(3) Antioxidants
There can, for example, be mentioned 2,6-di-tert-butyl-p-cresol,
2,5-di-tert-butylhydroquinone,
2,2'-methylene-bis(4-methyl-6-tert-butylphenol),
tetrakis(2,4-di-tert-butylphenyl), 4,4'-bisphenylenediphophonite,
4,4'-thiobis-(6-tert-butylphenol),
4,4'-thiobis-(6-tertbutyl-m-cresol),
octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenol) propionate.
etc.
(4) Ultraviolet absorbers
There can, for example, be mentioned
2-hydroxy-4-octoxybenzophenone,
2-(2'-hydroxy-5-methylphenyl)benzotriazole, ethyl
2-cyano-3,3-diphenylacrylate, etc.
(5) Antistatic agents
There can, for example, be mentioned polyethylene oxide,
carbowaxes, pentaerithritol monostearate, sorbitan monopalmitate,
sulfated oleic acid, etc.
(6) Lubricants
There can, for example, be mentioned calcium stearate, zinc
stearate, butyl stearate, polyethylene wax, palmitamide, stearyl
alcohol, ethylenebisstearamide, glycerol trimontanate, glycerol
hydroxystearate, etc.
(7) Coloring agents
There can, for example, be mentioned various kinds of dyeing lakes,
synthetic dyes, inorganic pigments, etc.
(8) Impact property improver
There can, for example, be metnioned MBS (methyl
methacrylate-butadiene-styrene), ABS, acrylic polymers fibrous
magnesium hydroxide, etc.
Compounding amounts of these additives (1) to (8) can appropriately
be selected, and, for example, there can be compounded in 100
weight parts of the halogen-containing resin 0.01 to 10 weight
parts of a heat stabilizer, 1 to 70 weight parts of a plasticizer,
0.01 to 2 weight parts of an antioxidant, 0.01 to 3 weight parts of
an ultraviolet abosrber, 0.01 to 2 weight parts of an antistatic
agent, 0.1 to 5 weight parts of a lubricant, 0.1 to 2 weight parts
of colorant and 1 to 20 weight parts of an impact property
improver.
There is no special restriction about the method and means to
compound components (a) to (d) and, if desired, various additives
in the halogen-containing resin in preparation of the resin
composition of the invention, and any method and means can be
adopted as long as respective components are uniformly compounded
in the resin thereby. For example, conventional means can be used
such as a ribbon blender high speed mixer, kneader, pleetizer or
extruder.
In the invention, the BET specific surface and the secondary gain
size means values measured by the following measurement methods,
respectively.
BET specifi surface area
BET specific surface area was determined by the three point
plotting method according to the nitrogen adsorption method,
provided that the molecular adsorption area of N.sub.2 was
calculated as (16,2 .ANG..sup.2). Further, each measurement sample
was first subjected to deaeration treatment in vacuo at 100.degree.
C. for 30 minutes, and then measured for adsorption isotherm of
nitrogen.
Secondray grain size
0.7 g of a sample is placed in a 100 ml beaker, and 70 ml of
deionized water is gradually added thereto to carry out sufficient
dispersion. Dispersion treatment is carried out 3 minutes using an
ultrasonic homogenizer. Immediately thereafter part thereof is
taken, and measured using a microtrack grain size analyzer produced
by LEEDS & NORTHROP INSTRUMENTS Company.
EXAMPLE
This invention is more detailedly described according to the
following examples.
EXAMPLES 1 TO 5
Polyvinyl chloride and other additives in the compounding ratio
indicated below were uniformly mixed with a Henschel mixer, and
melted and kneaded at 200.degree. C. using a monoaxial extruder.
The kneaded materials were press molded into a sheet 3 mm thick at
200.degree. C. and a pressure of 200 kg/cm.sup.2 for 5 munites
using a press molder, and test pieces were prepared therefrom.
______________________________________ Compounding
______________________________________ polyvinyl chloride 100
weight parts (average polymerization degree 1000) Hydrotalcite 0.1
weight parts Zinc stearate (Zinc compound) 0.2 weight parts
Stearoyl-benzoylmethane 0.2 weight parts (.beta.-diketone) MBS
(impact strength improver) 4.0 weight parts Epoxidized soybean oil
2.0 weight parts Lubricant 2.0 weight parts Processing auxiliary
1.0 weight parts Magnesium hydroxide varied amount
______________________________________
The hydrotalcite had the following composition
and in advance of use, was surface treated with 1 weight % stearic
acid and then heat treated at 240.degree. C. for 4 hours.
The magnesium hydroxide used was one which had been surface treated
with 1 weight % oleic acid and had BET specific surface area and
average secondary grain size shown in Table 1.
Each test piece was measured for initial coloring property by
visual observation, transparency by entire light beam
transmittance, and heat stability time as the time costed for the
test piece to blacken in an oven of 210.degree. C. These results
are shown in Table 1.
COMPARATIVE EXAMPLES 1 TO 3
The same manipulation as in Example 1 was made except that
magnesium hydroxide, which has the BET specific surface area and
average secondary grain size shown in Table 1 and surface treated
with 1 weight % oleic acid as in the case of Example 1, was used as
magnesium hydroxide. The results are shown in Table 1.
COMPARATIVE EXAMPLE 4
The same manipulation as in Example 1 was made exept that magnesium
hydroxide was not compounded. The results are shown in Table 1.
EXAMPLE 6
The same manipulation as in Example 1 was made except that, in
place of stearoyl-benzolymethane (.beta.-diketone), the same amount
of bisphenol A tetra C.sub.12-15 alkyl diphosphite (MARK 1500
produced by ADEKA ARGUS Co.) was used. The results are shown in
Table 1.
EXAMPLE 7
The same manipulation as in Example 1 was made except that as a
hydrotalcite was used one which has the following composition.
was used one which has the following composition.
and was surface treated with 1 weight % lauric acid. The results
are shown in Table 1.
EXAMPLE 9
The same manipulation as in Example 6 was made except that, in
place of bisphenol A C.sub.12-15 alkyl diphosphite, the same amount
of phenyl diisodecyl phosphite was used. The results are shown in
Table 1.
TABLE 1
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Magnesium hydroxide Physical properties of test piece BET specific
Average second- Compounding Initial Transparency (Entire Heat
surface area ary grain size amount coloring light beam transmit-
stability Number (m2/g) (.mu.m) (weight part) property tance) (%)
(min.)
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Example 1 25 0.3 0.1 no coloring 78 25 2 " " 0.2 " 74 30 3 " " 0.5
" 71 45 4 17 0.4 0.2 " 74 26 5 30 0.2 0.2 " 75 32 Comparative 10
1.0 0.2 " 70 17 example 1 2 60 8.2 0.2 yellow 62 24 3 6 19 0.2
yellow 58 17 4 -- -- 0 no coloring 79 15 Example 6 25 0.3 0.2 " 77
30 7 25 0.3 0.2 " 72 32 8 25 0.3 0.2 " 70 34 9 25 0.3 0.2 " 75 32
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